Substituted allyl phenols

ABSTRACT

COMPOUNDS OF THE GENERAL FORMULA   2-((R4-Z-(CH2)N-)M-C(-H(3-M))-),3-R3,4-R2,5-R1,6-R5-PHENOL   WHICH ARE USEFUL AS OXIDATION INHIBITORS, FUNGICIDES, ANTIMICROBIAL AGENTS AN CHEMICAL INTERMEDIATES AND PROCESS FOR PREPARING SAID COMPOUNDS.

United States Patent hoe 3,639,487 Patented Feb. 1, 1972 3,639,487 SUBSTHTUTED ALLYL PHENOLS Edward D. Weil, Lewiston, and Hans L. Schlichting, Grand Island, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y.

No Drawing. Original application Feb. 20, 1963, Ser. No. 260,076, new Patent No. 3,385,899, dated May 28, 1968. Divided and this application May 3, 1968, Ser.

Int. Cl. C07c 43/20 U.S. Cl. 260-613 R 17 Claims ABSTRACT OF THE DISCLOSURE Compounds of the general formula which are useful as oxidation inhibitors, fungicides, antimicrobial agents and chemical intermediates and processes for preparmg said compounds.

This is a division of copending parent application SN. 260,076 which was filed Feb. 20, 1963 now US. 3,385,899.

This invention relates to new phenolic compositions of matter and to processes for producing them. More specifically the present invention is concerned with novel sidechain substituted allyl phenols and to process for producing them.

The compositions of the present invention are useful as oxidation inhibitors, fungicides, antimicrobial agents and chemical intermediates.

The novel compositions of the present invention can be represented by the following general formula wherein the substituents R R R and R are each individually selected from the group consisting of hydrogen, halogen, alkyl from one to six carbon atoms, hydroxy, lower alkoxy, di(1ower a1kyl)amino, and nitro, with the total number of nitro groups being from zero to two, and where R is a substituent selected from the group consistof alkyl of from one to six carbon atoms, allyl, cyclohexyl, phenyl, chlorinated phenyl, nitrophenyl, hydroxyphenyl, bentyl, and lower acyl (one to six carbon atoms), Z is a substituent selected from the group consisting of oxygen, sulfur, S(=O), and SO Z being selected from oxygen and sulfur when R is acyl, m is an integer from zero to one, p is an integer from zero to one, and the sum of m and p is 1, and n is an integer from zero to one.

Illustrative examples of compounds of the present invention include, for instance; (a) o-allylphenol having the following substituent on the alpha-position of the allyl group: methoxymethyl ethoxymethyl isopropoxymethyl butoxymethyl amyloxymethyl hexyloxymethyl 2-methoxyethyl allyloxymethyl cyclohexyloxymethyl phenoxymethyl benzyloxymethyl p-chlorophenoxymethyl 2,4,5 -trichlorophenoxymethyl p-nitrophenoxymethyl methylthiomethyl ethylthiomethyl phenylthiomethyl p-chlorophenylthiomethyl acetoxymethyl butyroxymethyl hexanoyloxymethyl benzoyloxymethyl acetylthiomethyl methylsulfinylmethyl methylsulfonylmethyl p-chlorophenylsulfinylmethyl p-chlorophenylsulfonylmethyl 2-rnethoxyethy1 2-butoxyethyl 2-cyclohexy1oxyethyl Z-methylthioethyl 2-ethylthioethy1 Z-phenylthioethyl 2-benzy1thioethyl 2-p-chlorophenylthioethyl 2-acetylthioethyl 2-p-brornophenylthioethy1 trifluorocresoxymethyl (b) o-Methallylphenol having the above listed substituents on the gamma position of the methallyl group.

The following examples are listed to further illustrate the compositions included within the present invention.

2 1- [methoxymethyl] allyl) -3 -methylphenol 2- 1- [methoxymethyl] allyl) -4-methylpheno1 2-( 1- [methoxymethyl] allyl) -5-methylpheno'l 2-( l- [methoxymethyl] allyl -6-methylphenol 2- 1 [methoxymethyl] allyl) -3 ,4 (also 3,5; 3,6; 4,5; 4,6;

and 5, 6 -dimethylphenol 2- 1- [methoxymethyl] allyl) -5-methoxyphenol 2- 1- [methoxymethyl] allyl) -4 (dimethylamino) phenol 2-( 1- [methoxymethyl] allyl) 3 ,4,5-trimethy1phenol 2- 1- [methoxymethyl] allyl) -3 ,5 -dissopropylpheno1 2-( 1- [methoxymethyl] a1ly1)-3 -sec-amylphenol 2- 1- [methoxymethyl] allyl) -4,6-di-tert-butylphenol 2- 1-[methoxymethy1[allyl)-3 ,4, 6-trichlorophenol 2-( 1- [methoxymethyl] allyl) -4,6-dich1oropheno1 2-( 1- [methoxymethyl] allyl) -4-nitrophenol 2-( 1- [methoxymethyl] allyl) -4,6-dinitrophenol 2- 1- [Z-methoxymethyl] allyl) -5 -isopropylphenol 2-( 1- [2,4,5-trichlorophenoxymethyl] allyl) -3,4,6-

trichlorophenol 2- 1-[2,4-dich1orophenoxymethyl] allyl) -4,6-

dichlorophenol 2- l- [4-nitrophenoxymethyl] allyl-4-nitrophenol 2- 1- [methoxymethyl] allyl) -3 -hydr0xypheno1 2-( l- [methoxymethyl] allyl) -4-hydroxypheno1 2- 1- [3 -hydroxyphenoxymethy1] allyl) -3-hydroxypheno1 2-( 1- [methoxymethyl] allyl) -4-bromophenol The synthesis of the compositions of the present invention is accomplished by heating and thus rearranging ethers of the type which are new compositions of matter) may be made by reacting the appropriate phenols of the formula An alternative route to the ethers required as starting materials for the process of the invention is, first, to react a 4-halo-2-butenyl aryl ether of the structure R1 is OOH CH=CHCHzhalogen with at least one molar equivalent of a nucleophile MZR where M is a cation such as a metal (such as sodium) ammonium, or alkylammonium cation, preferably in an ionizing solvent (such as alcohol, water, dioxane, dimethylformamide, or the like), until the halogen is replaced by Z'R. This method is useful where the value of n in the product formula is zero.

The conversion of the ethers described above to the phenols is conducted by heating the ether to a temperature in the range of about 125 to 275 degrees centigrade, preferably 140-260 degrees centigrade, by itself or in the presence of an inert solvent such as N,N-diethylaniline, until a substantial conversion of the ether to a phenol occurs, generally requiring from about 5 minutes to about 1 week, depending on temperature. The reaction proceeds with rearrangement of the allyl radical onto the ring position ortho to the phenolic oxygen. A small amount of para substitution may accompany this principal reaction, and the products of the invention may contain minor amounts of isomeric impurities from this cause, such impurities being either separated or tolerated as harmless. The principal course of the rearrangement appears to be CHACHQMZ R R R or or R R R A further rearrangement may proceed concurrently and subsequently, to a greater degree as the temperature is raised or the time lengthened, to a lesser degree as the temperature is held near the lower end of the indicated range or as the reaction time is held to a minimum. This further rearrangement proceeds as follows Consequently the product may be a mixture of both side chain isomers, which difier only in the values of m and p in the general formula. The isomer where m is 1 and p is 0 generally predominates.

The process may be operated conveniently at or near atmospheric pressure, although lower and higher pressures may be utilized without departing from the scope of the invention. Where one or two of the groups R or R are to be nitro, it may be preferred to insert one or both nitro groups by subsequent nitration of the compound of the invention having hydrogen at the site where nitro is desired.

The novel phenols of the invention have a pronounced degree of biological activity, being fungicidal, bacteriostatic, and bacteriocidal. They also, especially where R R R and R are hydrogen or alkyl, have a high degree of antioxidant and stabilising activity and thus may be incorporated into petroleum oils and fuels, resins, elastomers, fats, greases, films, moldings, laminates, paints and other coatings and solvents to inhibit or prevent deterioration caused by air oxidation and thermal or photochemical deterioration of the substrate.

A preferred subgroup of the compounds of the invention is the group wherein R is hydrogen, R R and R are chosen from hydrogen and lower alkyl, 'R is lower alkyl, and Z, n, and p are as originally defined. This group is especially of interest as precursors of insecticidally active N-methylcarbamates described in a copending application filed on even date herewith. A second preferred subgroup of the compounds of the invention is the group wherein R is a phenyl group bearing the same substituents (i.e. R R R R as are present on the phenolic phenyl ring, Where n=0 and where Z is oxygen). These phenols are prepared especially readily by the process of the invention wherein the ether intermediate is symmetrical, thusly:

may be practiced the following specific examples are given.

EXAMPLE 1 A solution of 40 grams of trans-1,4-diphenoxy-2-butene and 200 cubic centimeters of N,N-diethyianiline was refiuxed for 7 hours then stripped under 0.4 millimeter pressure to remove diethylaniline. The residual oil was washed with dilute hydrochloric acid several times, then extracted with 200 cubic centimeters of 10 percent NaOH. The caustic solution was acidified, depositing an oil which was extracted with benzene, the benzene washed with water and dried over magnesium sulfate. The solution was then filteredsand evaporated, leaving 30 grams of product as an oil.

An'alysis.Calculated for 1-1 0 neutralization equivalent 240. Found: (potentiometric titration with tet- 6 EXAMPLE 5 T o a solution of 6 grams of sodium methoxide and 7 grams of ethyl mercaptan in 100 cubic centimeters of methanol was added 18.3 grams of 1-ch1oro-4-phenoxyrabuty'lammonium hydroxide in pyridine) 5 Z-butene. After standin overni ht, the solution was added The infrared Spectrum of the product showed f f of to water, the oil extra cted wih ether, dried over magaboul equal Strength. Wave lengths charactenstlc of nesium sulfate, and evaporated free of ether leaving 1- termial and nontermmal groups also both ethylthio-4-phenoxy-2-butene as a colorless oil, boiling and 2 balms were: evldence' The product conse' point 90 to 93 degrees centigrade (0.08 millimeter). quemly 1S a mlxmre of I and H 10 Analysis.-Calculated for C H OS (percent): S, 15.4.

OH CHZCH2 OH CH3 Found (percent): S, 15.0.

g fl EXAMPLE 6 \CHQO a \CH=CHO A solution of 14 grams of the product of Example 5 in 15 50 cubic centimeters of diethylaniline was refluxed for I II 10 hours, then worked up as in Example 1 to obtain 12 By conducting the reaction at 165 degrees centigrade, a fi of phenom havmg the correct neutrahzatlon quivalent for C H OS. phenolic product predominantly having the band characteristic of CH=CH groups is obtained. 20 EXAMPLE 7 EXAMPLE 2 The product of Example 6 (4 grams) was allowed to stand in cubic centlmeters of benzene with 1.5 grams Five grams of the product of Example 1, 1.5 grams of of methyl isocyanate for 4 days, then the mixture was methyl isocyanate, 20 Cubic celltlmetels of benzene, and 1 stripped to 100 degrees centigrade at 0.01 millimeter presp of dibutyltin laufate were mixed and let Stand for 25 sure leaving a brownish oil. A potentiometric titration 0116 hOIlI- The mixture Was then Y -p f f leaving the demonstrated the absence of the phenolic group. The incarbamate as an oil. Potentiometnc tltration indicated frar d spectrum indicated the carbamate carbonyl group the phenolic group to be absent. (b d at 5 7 i Analysis.Calculated for C H O N (percent N, 4.72. Found (percent): N, 4.79. EXAMPLE 8 On prolonged standing, the oil partly crystallized. The To a solution of 6 grams of sodium methoxide and 12.5 crystals were removed and recrystallized from benzenegrams of thiophenol in 100 cubic centimeters of methanol heptane to obtain a colorless solid, melting point 66 to was added 18.3 grams of 1 phenoxy-4-chloro-2-butene. 67 degrees centigrade. Infrared analysis showed essential- After standing overnight, the reaction mixture was poured ly none of the -CH=CH band at 915 crnf conseinto water. The product came out as colorless crystals quently this crystalline product was substantially the pure which were washed with water, then recrystallized from isomer having the CH(CH )OH=CHOC H side chain. aqueous ethanol to obtain 18.5 grams colorless platelets,

melting point 50 to 51.5 degrees centigrade. EXAMPLE 3 Analysis.Calculated for C H OS (percent): S, 12.5. To a solution of 10 grams of sodium methoxide in 1 00 Found (Percent): cubic centimeters of methanol was added 18.3 grams of EXAMPLE 9 trans-1-chloro-4-phenoxy-2-butene, then the mixture was refluxed for several hours, stripped free of methanol under A Solution of 14 grams of the PY of Example 8 reduced pressure and the residue added to water. The r m Cubic centimeters of N,N-dlethylaniline Was organic oil was extracted with ether, dried over soda ash, fluxed under mtrogen for 10 hours, then Worked P as and then stripped free of ether under reduced pressure 1n m e 1 t0 ebtaill a Phenolic Oil having the Correct leaving 15.5 grams of 1-methoxy-4-phenoxy-Z-butene as neutralllatlon equlvalent for CIGHIGOS' a colorless oil.

A solution of 14 grams of 1-meth0xy-4-phenoxy-2- 50 EXAMPLE 10 butene in 50 cubic centimeters of diethylaniline was re- The reaction of the Prodllet of Example 9 With methyl fluxed for 13 hours, then the product isolated as in EX- isocyanate Was Conducted as in Example 7 to Obtain the ample 1 to obtain 8.5 grams of colorless phenolic oil. desired eafbamate as a brownish The infrared spectrum indicated it to be predominantly Analysis--calculated for C18H19O2SN (P the o-substituted phenol having the Found (P CH(CH OCH )CH=CH EXAMPLES 1116 side cham' EXAMPLE 4 Following the procedure of Example 3, 0.1 portions of trans 1 chloro 4 phenoxy 2 butene was reacted Five grams of the product of Example 3, 2 grams with substantially equimolar amounts of various sodium methyl isocyanate, 1 drop dibutyltin laurate, and 50 cubic alkoxides in excess of the alcohols corresponding to the centimeters benzene were refluxed for one hour, then alkoxides. In each case, after at least 40 hours at room stripped to degrees centigrade under aspirator vacutemperature (except for initial spontaneous exotherm) the um, leaving the product as a colorless oil. reaction mixtures were stripped free of the alcohol, the Analysis.Calculated for C H O N (percent): N, residues washed with water, and the organic oil distilled. 5.96. Found (percent): N, 5.7. d The yields and properties of the products are as follows:

Yield N0. Ether (g.) Properties 11E 1-ethoxy-4-phenoxy-2 butene 15 Oil, B.P. 8690 (0.05 mm.). l-isopropoxy-4-phenoxy-2-butene. 13 Oil, B.P. 8490 (0.15 mm.). l-n-butoxy-4phenoxy-2-butene 15 Oil, B P 107-110 (0 25 mm l-prl-amyloxyi-phenoxy-2-butene 17. 5 011, 3.1. 110-114 (0.1 mm) 1-cyc1ohexyloxy-4-phenoxy-Z-butone 11 Oil, 13.1. 120.5-123 (0.15 16E 1-(2-methoxyethoxy)-4-phenoxy-2-butene .Q..- 15 0i l f l l 107111 (0.1 111111.).

Each of these products was rearranged to the corresponding alkoxybutenyl phenol by heating without solvent under nitrogen in a vessel immersed in a vapor bath at 230.to 240 degrees centigrade.

structure and at 975 cm.- indicating the CH CH CH=CHOR structure, predominantly the former.

TABLE Derived Percent Percent No. Carbamate* irom- Physical form N calcd. N found 110 llP Light brown syrup 5. 6 5. 1

O C ONHCH C HBO 02H;

\ O C ONHCHz CAHEO CI-I(CH3)2 13C 131 Straw-colored syrup 5. 1 5.

O C O NH CH3 C H5O OHzCI-IzCHzCHs O C O NH CH C4H5O C5H11D1l 150 151 Reddish-brown syrup... 4. 6 4. 5

O C O NHCHz o Hao-cyclo-CaHn 16G 161 Light brown syrup 5. 0 5. 1

O C O NH CH3 CgHnO CHzCHzO CH3 *-O H in these formulae refers to the mixture of isomeric side chains OH(CH=CH CH2- and CH(CH OH=OH, predominating in the former.

All the above phenols showed substantialy the correct neutralization equivalent when potentiometrically titrated with 0.1 N tetrabutylammonium hydroxide in pyridine solution. The infrared spectra of these products exhibited a a band at 915 cm." indicating the Each of the above phenols (1 part by weight) was allowed to stand for one day with 0.5 part by weight of methyl isocyanate plus a catalytic amount (1%) of dibutyltin dilaurate, then stripped to about 120 degrees centigrade under 0.1 millimeter pressure to remove excess isocyanate. The products remained as undistilled syrups.

EXAMPLE 17 To a solution of grams of sodium methoxide and 22 grams methyl mercaptan in 250 cubic centimeters methanol was added 18.3 grams of 1-chloro-4-phenoxy-2- butene, causing a vigorous exotherm. When the reaction subsided, the mixture was refluxed for one hour, then stripped under vacuum to remove alcohol. The product was taken up in benzene, washed with water, stripped A free of benzene, and distilled to obtain 16 grams of lmethylthio-4-phenoxy-2-butene as a nearly colorless oil, boiling point 104 to 105 degrees centigrade (0.15 mm.).

Analysis.Calculated for C H OS (percent): S, 16.5. Found (percent): S, 16.2.

This sulfide was rearranged to the corresponding phenol.

To a solution of 47 grams of phenol and grams of sodium hydroxide in 200 cubic centimeters of ethanol was added 21 grams of a mixture of roughly equal amounts of CH OCH CH CH=CHCH Cl and (obtained by the known addition of chloromethyl methyl ether to butadiene in the presence of zinc chloride). The solution was refluxed for minutes, then evaporated 9 to a pot temperature of 100 degrees centigrade, water then added to dissolve the salts, and the organic oil separated off. The oil was distilled at 100 to 120 degrees centrigrade (1.5 mm.). In frared examination showed it was principally CH OCH CH CH=CHCH OC H with a very minor amount of This ether was converted to the corresponding phenol by heating at 234 to 240 degrees centigrade for 1 hour. The product was a light amber oil, neutralization equivalent 205 (theory 192, therefore 94% pure). The phenol was found by infrared examination to have both the CH(CH=CH )CH CH OCH 1 and CH(CH )CH=CHCH OCH side chain isomers present, but predominantly the former. The phenol was converted to the corresponding N-methylcarbonate by warming at 40 degrees centigrade for 1 hour with /3 its volume of methyl isocyanate in the presence of 1 to 2 percent triethylene diamine catalyst. It was then freed of excess isocyanate by Warming to 120 degrees centigrade at 0.1 millimeter, leaving the carbamate as a light tan syrup having the correct nitrogen analysis and showing the carbamate carbonyl and NH bands in the infrared spectrum.

EXAMPLE 19 1,4-bis(p-cresoxy)-2-butane (I) was obtained by refiuxing 11 grams sodium methoxide in 100 milliliters methanol with 21 grams p-cresol and then adding 13 grams trans-1,4-dichloro-2-butene; yield 90 percent of colorless crystalline solid, melting point 118 degrees Centigrade.

A solution of 8 grams of this intermediate in 8 grams N, N-diethylaniline was refluxed for four hours, then stripped under 0.5 millimeter pressure to remove diethylaniline. The residue was washed with dilute hydrochloric acid several times, then recrystallized from ethanol to yield 7 grams of the corresponding cresoxybutenyloresol (IV), a colorless solid, melting point 105 degrees centigrade.

Treating a solution of 5 grams of this phenol in 10 milliliters benzene with methyl isocyanate as described in Example 2 yields the corresponding p-cresoxy butenylcresyl N-methylcarbamate, 5 grams of colorless solid,

10 melting point 102.5 to 103 degrees centigrade (from heptane).

Analysis.Calculated for C H O N (percent): N, 4.31. Found (percent): N, 4.46.

EXAMPLE 20 To a solution of 11 grams sodium methoxide in milliliters ethanol was added 21 grams p-cresol and then 25 grams trans-1,4-dichloro-2-butene. After refluxing for two hours, the reaction mixture is poured into ether. A distillation yields 15 grams trans-l-chloro-4-p-cresoxy-2- butene, a colorless liquid, boiling point 100 to degrees centigrade (0.3 mm.), n 1.5378. As by-product there is formed 5 grams of 1,4-bis(p-cresoxy)-2-butene identical with that described in the preceding example.

Trans-1-chloro-4-p-cresoxy-2-butene is converted into 1-methoxy-4-p-cresoxy-Z-butene, by reacting with sodium methoxide similarly as described in Example 3, to obtain a colorless liquid, boiling point 95 to 100 degrees centigrade (0.05 mm.), n 1.5166. Heating 20 grams of this ether up to 230 degrees centigrade for three hours yields on distillation 12 grams of the corresponding methoxybutenyl-p-cresol, a colorless liquid, boiling point to degrees Centigrade (0.05 mm.), n 1.5640.

Treatment of this cresol in benzene solution gives methoxy-butenyl-p-cresyl N-methylcarbamate as an oil. Potentiometric titration indicated the phenolic group to be absent.

Analysis.--Calculated for C H O N (percent): N, 5.62. Found (percent): CI, 5.60.

EXAMPLE 21 To a solution of 11 grams sodium methoxide in 100 milliliters methanol was added 26 grams trans-1,4-dichloro-Z-butene, then the mixture was refluxed for 1 hour, poured into 500 milliliters water, and extracted with ether. The organic layer was dried over calcium chloride and then distilled to yield 16 grams 1-chloro-4-methoxy-2- butene, boiling point 70 to 72 degrees centigrade (13 mm.), D 1.004, n 1.4484.

Analysis-Calculated for C H OCl (percent): Cl, 29.46. Found (percent): Cl, 29.5.

Refluxing 1-chloro-4-methoxy-2-butene With an equimolar amount of the sodium salts of the corresponding phenols in benzene/ ethanol yields the following methoxybutenyl aryl ethers as summarized in the following table.

TABLE'Continued Yield B.P. 0.)]

No. Structure (percent) mm. 70

5 ?OH2CH=CHOH2OOH3 83 reg-1121 1.5326

6 ?CH2CH=CHCH:OCH3 70 3485150] 1.5070

(CHmOH CH(CH3)2 EXAMPLE Analysis.-Calculated for C H O Cl (percent): C1,

The methoxybutenyl aryl ethers as described in the preceding example are heated up to 230 to 235 degrees centi- 20 grade for three hours, and then stripped free of ether under reduced pressure, leaving the rearranged phenol derivative behind. These phenols are converted into N- methylcarba-mate's by treatment with methyl isoeyanate as described in Example 2.

22.8. Found (percent): Cl, 22.4.

Heating of this diether up to 230 to 240 degreescentigrade for four hours, yields a phenol, which may be purified by dissolving in 2 N NaOH-solution and extracting the unreacted neutral portions with ether. Addition of dilute sulfuric acid to the aqueous layer gives 2- (p-chlorophenoxybutenyl) p chlorophenol, which may be is TAB LE N, analysis Physical N0. Structure R=0 C ONE 0 H; appearance Calculated Found l /CH=CH2 0 H20 C H;

| /CH=CH2 0 H2 0 C H; H3C

I /C H=CH2 CHzO CH: (0 Ha) 20 H- 4 R Wax 5. 20 5.

l CH=CH1 CHZO CH:

i /C H; 0 H2 /OH=CH 0 H20 C H3 (0 H3) 20 H- CH(CH3) 2 Principal isomer, accompanied by minor amount of 'y-methoxymethallyl isomer.

EXAMPLE 23 lated by ether extraction. Treating this phenol in trichloroethylene with methyl isocyanate gives the desired 2-(pchlorophenoxybutenyl) p chlorophenyl N methylcarbamate.

Analysis.-Calculated for C H O CI N (percent): N,

3.85; CI, 19.4. Found (percent): N, 3.78; CI, 19.2.

1 3 EXAMPLE 24 Fungicidal activity Bean plants (Tendergreen variety) were sprayed with an aqueous dispersion of 2-(1-[methoXymethyl]allyl)-4 methylphenol at 0.04 percent concentration and then infested heavy with spores of bean mildew. Some unsprayed plants were also infested at the same time. About one week later, when the latter plants were heavily mildewed, the sprayed plants were 100 percent free of the disease symptoms.

EXAMPLE 25 Bacteriostatic activity Staphylococcus aureus spores inoculated onto nutrient agar containing 0.01 percent of the following phenols are found not to propagate to a measurable degree:

2-( l-[4-chlorophenoxy1allyl) -4-chlorophenol 2- 1-[2,4dichlorophenoxy] allyl) -4,6-dichlorophenol 2-( l- [2,4,5-trichlorophenoxy] allyl) -3,4,6-trichlorophenol 2- l- [4-nitrophenoxy] allyl) -4-nitrophenol 2-( 1- [methoxymethyl] allyl) -4-chlorophenol 2-( 1- [methoxymethyl] allyl --hexyloxyphenol EXAMPLE 26 Fungicidal activity Cotton seeds are treated with 6 ounces of the following compounds per 100 pounds (the chemicals are formulated as 50 percent wettable powders by grinding with 45 percent clay, 3 percent ligninsulfonate dispersing agent, and 2 percent naphthalenesulfonate wetting agent):

2- 1- [4-chlorophenoxy] allyl) -4-chloro phenol 2- l- [2,4-dichlorophenoxy] allyl) -4, fi-dichlorophenol 2-( 1- [2,4,5 -trichlorophenoxy] allyl) -3,4,6-trichloro phenol 2-( 1- [4-nitrophenoxy] allyl -4-nit1'ophenol 2- 1- [methoxymethyl] allyl -4-chlorophenol 2- 1- [methoxymethyl] allyl) -5-hexyloxyphenol The treated seeds are then planted in soil heavily infested with Rhizoctonia and Fusarium fungi, Untreated seeds also planted in the same soil largely fail to yield viable seedlings because of damping-01f, whereas the treated seeds yield a healthy stand of cotton seedlings.

The phenols of the invention also have utility as stabiliz ing additives, as shown by the following example.

EXAMPLE 27 Antioxidant activity A sample of polyethylene is milled with 0.05 percent by weight of 2-(1-[methoxymethyl]allyl) -6-tert-butylphenol. The milled sample is then placed in a vessel at 150 degrees centigrade in an atmosphere of oxygen and the volume of oxygen absorbed is followed manometrically. The sample containing the additive is found to exhibit a lengthy induction period before any substantial oxygen uptake occurs whereas the polyethylene without the additive begins to take up oxygen at a rapid rate almost immediately.

14 What is claimed: 1. A compound of the formula wherein (a) R, R R and R are selected from the group consisting of (1) hydrogen, (2) up to but no more than 3 of R R R and R are chlorine and the remaining are hydrogen; (3) no more than one of R R R and R is a nitro group and the remaining are hydrogen, and (4) no more than one of R R R and R are hydroxyl and the remaining are hydrogen;

(b) R is selected from the group consisting of phenyl,

mononitrophenyl, monohydroxyphenyl, monochlorophenyl, dichlorophenyl, and trichlorophenyl; and

(c) m and p are integers of from 0 to 1, the sum of m and p being 1.

2. The compound of claim 1 wherein one of R R R and R substituents is a nitro group.

3. The compound of claim 1 wherein one of R R R and R5 is a hydroxyl group.

4. The compound of claim 1 wherein R R, R and R are hydrogen.

5. The compound of claim 1 wherein R is phenyl.

6. The compound of claim 1 wherein R is mononitrophenyl.

7. The compound of claim 1 wherein R is monohydroxyphenyl.

8. The compound of claim 1 wherein up to but no more than three of R R R and R substituents are chlorine, the remaining are hydrogen.

9. The compound of claim 1 wherein R is trichlorophenyl.

10. The compound of claim 1, wherein m is 1.

11. The compound of claim 1, wherein R R R and R are selected from the group consisting of hydrogen, chlorine, and nitro.

CH=CH 14. The compound 2-(l-[2,4,S-trichlorophenoxymethyl]allyl)-3,4,6-trichlorophenyl, that is, the compound of the structure 15 16 15. The compound 2-(1-[2,4-dichlorophenoxymethyl] 17. The compound 2- (1 [3-hydroxyphenoxymethyl] allyl)-4,6-dichlorophenol, that is, the compound of the al1y1)-3-hydroxyphenol, that is, the compound of the structure 7 structure H=om C1 10 \OH 16. The compound 2-(1-[4-nitrophenoxymethyl]al1yl)- 4-nitrophenol, that is, the compound of the structure I I References Cited -cH om-o-@-o1vo2 15 UNITED STATES PATENTS (JH=OH, 2,378,698 6/1945 Gibbs 260613 2,488,501 11/1949 Moyle 260-613 1 N01 20 BERNARD HELFIN, Primary Examiner 333 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,639387 Dated February I 197 Inventor) Edward D. Neil and Hans L. Schl ichting It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1 line +5, "CH=CH should read --CH=CH( p line 1 56, bentyl should read --benzyl Col umn- 3, line 1 l 'XCH CH-CHCH should read ---XCH CH=CHCH line 16, "CH -CH-" should read ---CH =EH- line 22 XCH CH-" shoul d read ---XCH CH= Column line 8, fiR

should read line 22, insert ---The rearrangement reaction of the ethers described above can also be conducted with essentially sole formation of the phenolic products of the invention where m is l and p is 0 by subjecting the said ethers to a Lewis acid catalyst, such as boron halides, especial ly boron trichloride at about 30 to l00C.---. Column 6, line 57 "3,0.l portions" should read ---3,0.l mole portions- Column 7, line 5 "C HQOC CH CH CH should read ---CL H60CH2CH2CH2CH i 75, "CH( H=CHz)" 5h ul rgadv =CH(CH-CH Column 10, last formula CHCH 0CH should read CHCH 0CH Column 1 line 6, that part 0; the formula C x should read -CH:

Signed and sealed this 25th day of July 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROERT GO'I'TSCHALK Attesting Officer Commissioner of Patents 

